Driver for electrochromic element, method for driving electrochromic element, optical filter, imaging device, lens unit, and window component

ABSTRACT

A driver for an electrochromic element is configured to adjust the transmittance of a solution-type electrochromic element to allow the element to display a tone. The element has a pair of electrodes and at least one organic electrochromic material mixed between the electrodes. The driver has an adjusting controller configured to adjust the transmittance of the element. The adjusting controller has controller A and controller B. Controller A is configured to saturate a change in the transmittance of the element to an initial state by applying the voltage which resets the element to the initial state. Controller B is configured to control the tone of the element by applying the voltage which adjusts the transmittance of the element following controller A.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.14/296,307, filed Jun. 4, 2014, which claims the benefit of JapanesePatent Application No. 2013-120805, filed Jun. 7, 2013, and JapanesePatent Application No. 2014-099901, filed May 13, 2014, which are herebyincorporated by reference herein in their entirety.

BACKGROUND OF THE INVENTION Field of the Invention

The present invention relates to a driver for an electrochromic element,a method for driving an electrochromic element, an optical filter, animaging device, a lens unit, and a window component. In particular, thepresent invention relates to a driver for an organic electrochromicelement configured to adjust the tone of the element, a method fordriving an organic electrochromic element with such a driver, and anoptical filter, an imaging device, and a window component in which sucha driver is used.

Description of the Related Art

Electrochromism (EC) is a phenomenon in which a reversibleelectrochemical reaction (oxidation or reduction) induced uponapplication of voltage changes the optical absorption range of asubstance and thereby makes the substance colored or colorless. Anelectrochemically colored/erased element that works on electrochromismis referred to as an electrochromic (EC) element and is expected to beused as a light-controlling element with varying light transmittance.

Known EC elements include ones in which a metal oxide, such as WO₃, isused as EC material, EC elements in which a conductive polymer is used,and EC elements in which an organic small molecule, such as viologen, isused. In particular, an organic EC element in which alow-molecular-weight organic material turns colored/colorless in theform of solution is known to have advantages such as a sufficiently highcontrast ratio in the colored state and high transmittance in thecolorless state. This type of EC element is also known to beadvantageous in that it can have any desired color tone by containingmultiple materials with different absorption wavelengths.

The use of an EC element in an optical filter requires tone controldrive that allows for the control of the amount of light that passesthrough the filter. As a driving method for tone control, JapanesePatent Laid-Open No. 11-109423 discloses a PWM driving method thatincludes applying a voltage pulse. In this driving method the tone iscontrolled through the control of the durations per pulse for which theoxidation and the reduction of the organic EC material proceed.

Japanese Patent Laid-Open No. 11-316396 discloses a method forpreventing EC material in an EC element from remaining colored at thestart of service of the EC element, and this method includes resettingthe EC element to the initial state at the start or end of service ofthe element.

A non-patent document (Michael G. Hill, Jean-Francois Penneau, BaruchZinger, Kent R. Mann, and Larry L. Miller, “Oligothiophene CationRadicals. π-Dimers as Alternatives to Bipolarons in OxidizedPolythiophenes,” Chemistry of Materials, 1992, 4, 1106-1113) reports amaterial whose radical species forms an assembly while the material iscolored through oxidation.

The control of the tone of an organic EC element through quantitativeregulation of electrochemical reaction has been found disadvantageousbecause of the following problems that occur with a single material orbetween multiple materials.

As disclosed in the aforementioned non-patent document, some materialshave a radical species that forms an assembly (a dimer) while thematerial is colored through reaction. The electronic state of such anassembly is different from that of the radical species of the material,and thus the radical form and the assembly exhibit different absorptionprofiles. Research by the inventors has found that the absorptionspectrum of such a material varies because the behavior of absorptionchanges of the radical species and the assembly during coloring isdifferent from that during erasing. It is therefore difficult to controlthe tone while maintaining the absorption spectrum in both directions,i.e., the coloring direction and the erasing direction, when using amaterial that forms an assembly.

In cases where multiple materials are mixed that turn into cationthrough oxidation from the neutral state and return to the neutral statethrough back reduction, the absorption ratios between the materialsduring coloring are different from those during back reduction becausethe materials have different oxidation voltages and their oxidized formshave different back reduction voltages. In general, oxidation of amaterial is more likely to occur with increasing positive differencebetween the oxidation voltage of the material and the voltage of theelectrode that acts on the material, and back reduction is more likelyto occur with increasing negative difference between the back reductionvoltage of the material and the voltage of the electrode that acts onthe material. Trying to oxidize multiple materials together thereforeresults in the material that has the lowest oxidation voltage going intoreaction faster than all other materials, which have higher oxidationvoltages. When back-reducing the cations as oxidized forms of multiplematerials together, however, the reaction is not advantageous to thesame material because the back reduction voltage of this material islower than that of the other materials.

SUMMARY OF THE INVENTION

As a solution to the problems described above, a driver for anelectrochromic element is a driver configured to adjust thetransmittance of a solution-type electrochromic element to allow theelement to display a desired tone. The element has a pair of electrodesand at least one organic electrochromic material mixed between theelectrodes.

The driver has an adjusting controller configured to adjust thetransmittance of the element. The adjusting controller has controller Aand controller B. Controller A is configured to saturate a change in thetransmittance of the element to an initial state by applying the voltagewhich resets the element to the initial state, and controller B isconfigured to control the tone of the element by applying the voltagewhich adjusts the transmittance of the element following controller A.

Further features of the present invention will become apparent from thefollowing description of exemplary embodiments with reference to theattached drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram that illustrates an embodiment of an ECelement according to an aspect of the invention.

FIG. 2 is a schematic diagram that illustrates an embodiment of anEC-element driver according to an aspect of the invention.

FIGS. 3A and 3B are diagrams that illustrate absorption spectra of amaterial that forms an assembly.

FIGS. 4A and 4B are diagrams that illustrate absorption spectra of an ECelement that contains multiple materials, the EC element driven at afixed voltage.

FIG. 5 is a diagram that illustrates a form of drive control used inExample 1 of the invention.

FIG. 6 is a diagram that illustrates the change with time of the 630-nmabsorption of an EC element that contains multiple materials in pulsewidth modulation drive.

FIG. 7 is a diagram that illustrates a form of drive control used inExample 2 of the invention.

FIG. 8 is a diagram that illustrates a form of drive control used inExample 3 of the invention.

FIG. 9 is a schematic diagram that illustrates a lens unit in which anoptical filter according to an aspect of the invention is used and animaging device that has this lens unit.

FIG. 10 is a schematic diagram that incorporates an optical filteraccording to an aspect of the invention.

FIGS. 11A and 11B illustrate a window component that has an EC elementaccording to an aspect of the invention.

DESCRIPTION OF THE EMBODIMENTS

The following describes some aspects of the invention in detail.

A driver according to an aspect of the invention for an electrochromic(EC) element is a driver configured to adjust the transmittance of asolution-type electrochromic element to allow the element to display adesired tone. The element has a pair of electrodes and at least oneorganic electrochromic material mixed between the electrodes.

The driver has an adjusting controller configured to adjust thetransmittance of the element. The adjusting controller has controller Aand controller B. Controller A is configured to saturate a change in thetransmittance of the element to an initial state by applying the voltagewhich resets the element to the initial state, and controller B isconfigured to control the tone of the element by applying the voltagewhich adjusts the transmittance of the element following controller A.

The following describes some embodiments of the invention in detail withreference to drawings.

FIG. 1 is a schematic diagram that illustrates an embodiment of an ECelement according to an aspect of the invention. As illustrated in FIG.1, an EC element according to an aspect of the invention has a structurein which a pair of transparent substrates 2 and 6 with a pair oftransparent electrodes 3 and 5 are joined together with spacers 4therebetween in such a manner that the surface of one electrode shouldface that of the other. This structure also includes an EC layer 7,which is a solution of an electrolyte and the organic EC material in asolvent, located in the space defined by the pair of transparentelectrodes 3 and 5 and the spacers 4.

The transparent electrodes 3 and 5 are connected to a drive power supply8. Applying voltage across the electrodes brings the organic EC materialinto electrochemical reaction.

Examples of electrochromic elements (also abbreviated to “EC elements”)include ones in which the electrochromic material (also abbreviated to“EC material”) is an inorganic material and ones in which the ECmaterial is an organic material. An organic electrochromic element (alsoabbreviated to “organic EC element”), in which the EC material is anorganic material, is preferred in particular.

In general, an organic EC material is neutral and does not absorb lightin the visible region when no voltage is applied. An EC element exhibitshigh transmittance in such a colorless state. Applying voltage acrossthe electrodes induces electrochemical reaction in the organic ECmaterial, making the material in the neutral state oxidized (cation) orreduced (anion). In a cationic or anionic state, an organic EC materialabsorbs light in the visible region and has a color. An EC elementexhibits low transmittance in such a colored state.

Hereinafter, the reaction through which a neutral EC material isoxidized and forms cation is referred to as oxidation, and the voltageat which the oxidation occurs is referred to as oxidation voltage. Thereaction through which the cation returns to the neutral state isreferred to as back reduction, and the voltage at which the backreduction occurs is referred to as back reduction voltage. Likewise, thereaction through which a neutral EC material is reduced and forms anionis referred to as reduction, and the voltage at which the reductionoccurs is referred to as reduction voltage. The reaction through whichthe anion returns to the neutral state is referred to as back oxidation,and the voltage at which the back oxidation occurs is referred to asback oxidation voltage.

When the EC element is used in a light-controlling element, the ECelement may retain high transmittance in the colorless state so that theeffects on the optical system can be minimized. The transparentsubstrates and the transparent electrodes may therefore be made of amaterial sufficiently permeable to visible light.

The transparent substrates 2 and 6 are typically made of a glassmaterial and can be optical glass substrates made of Corning #7059 orBK-7, for example. Plastic, ceramic, and similar materials can also beused as appropriate if they have sufficient transparency. Thetransparent substrates are preferably made of a material that is rigidand unlikely to be strained, more preferably with low flexibility. Thethickness of the transparent substrates is typically from several tensof micrometers to several millimeters.

The transparent electrodes 3 and 5 can be made of a material that hashigh optical transparency with respect to light in the visible regionalong with high conductivity. Examples of such materials include metalsand metal oxides such as the indium tin oxide alloy (ITO), tin oxide(NESA), indium zinc oxide (IZO), silver oxide, vanadium oxide,molybdenum oxide, gold, silver, platinum, copper, indium, and chromium,silicon-based materials such as polysilicon and amorphous silicon, andcarbon materials such as carbon black, graphite, and glassy carbon.Conductive polymers with improved electrical conductivity resulting fromdoping or other treatment (e.g., complexes of polyaniline, polypyrrole,polythiophene, polyacetylene, polyparaphenylene, orpolyethylenedioxythiophene (PEDOT) and polystyrene sulfonate) can alsobe used. An EC element according to this embodiment of the invention mayhave high transmittance in the colorless state, and the electrodes insuch an EC element can be made of ITO, IZO, NESA, or a conductivepolymer with improved electrical conductivity in particular becausethese materials do not absorb light in the visible region. Suchmaterials can be used in various forms, such as bulk or fine particles.Such electrode materials can be used alone or in combination.

The EC layer 7 is a solution of an electrolyte and the organic ECmaterial in a solvent.

The solvent can be of any kind in which the electrolyte is soluble andcan be a polar one in particular. Specific examples include water andorganic polar solvents such as methanol, ethanol, propylene carbonate,ethylene carbonate, dimethylsulfoxide, dimethoxyethane, acetonitrile,γ-butyrolactone, γ-valerolactone, sulfolane, dimethylformamide,dimethoxyethane, tetrahydrofuran, propionitrile, dimethylacetamide,methylpyrrolidinone, and dioxolane.

The electrolyte can be of any kind of ion-dissociative salt that isreasonably soluble and contains a cation or anion electron-donativeenough that the organic EC material can be colored. Examples includeinorganic ion salts such as alkali metal salts and alkaline-earth metalsalts, more specifically, alkali metal salts that contain Li, Na, or K,including LiClO₄, LiSCN, LiBF₄, LiAsF₆, LiCF₃SO₃, LiPF₆, LiI, NaI,NaSCN, NaClO₄, NaBF₄, NaAsF₆, KSCN, and KCl, and quaternary ammoniumsalts and cyclic quaternary ammonium salts, including (CH₃)₄NBF₄,(C₂H₅)₄NBF₄, (n-C₄H₉)₄NBF₄, (C₂H₅)₄NBr, (C₂H₅)₄NClO₄, and(n-C₄H₉)₄NClO₄. Such electrolyte materials can be used alone or incombination.

The organic EC material can be of any kind that is soluble in thesolvent and can express colored and colorless conditions throughelectrochemical reaction. It is possible to use a knownoxidation-/reduction-colorable EC material. When the EC element is usedin a light-controlling element, transmittance contrast and wavelengthflatness are required. The organic EC material can therefore be amaterial that exhibits as high transmittance as possible in thecolorless state and offers a high coloring efficiency (the ratio of theoptical density to the amount of charge injected) for the sake of theserequirements. It is also possible to use a combination of multiplematerials for wavelength flatness if it is difficult to obtain flatabsorption with one material.

Specific examples of organic EC materials that can be used includeorganic dyes such as quinone dyes, viologen dyes, srylyl dyes, fluorandyes, cyanine dyes, and aromatic amine dyes and organic metalliccomplexes such as metal-bipyridyl complexes and metal-phthalocyaninecomplexes.

It is also possible to use a dispersion of an inorganic EC material in asolution. Examples of inorganic EC materials include tungsten oxide,vanadium oxide, molybdenum oxide, iridium oxide, nickel oxide, manganeseoxide, and titanium oxide.

The EC layer 7 can be liquid or gel. The EC layer 7 can be used in theform of a solution configured as above and can also be used in the formof gel. Adding a polymer or a gelling agent to solution turns thesolution into gel. Examples of such polymers (gelling agents) include,but are not limited to, polyacrylonitrile, carboxymethylcellulose,polyvinyl chloride, polyvinyl bromide, polyethylene oxide, polypropyleneoxide, polyurethane, polyacrylate, polymethacrylate, polyamide,polyacrylamide, polyester, polyvinylidene fluoride, and Nafion. In thisway, viscous solution or gel, for example, can be used as the EC layer7.

A transparent structure with a flexible meshwork (e.g., a spongystructure) that carries a solution can also be used as well as a mixturelike the above one.

FIG. 2 is a schematic diagram that illustrates an embodiment of anEC-element driver according to an aspect of the invention. A driveraccording to this embodiment of the invention for an EC element has anEC element 1, a drive power supply 8, a resistor switch 9, and anadjusting controller 10.

The drive power supply 8 applies voltage V1 for resetting the EC elementto an initial state and a driving voltage V2 for the display of adesired tone by the EC element. The application of V1 and V2 may be donewith separate drive power supplies.

The resistor switch 9 connects one of a resistor R1 and a resistor R2,which is of higher resistivity than the resistor R1, in series in aclosed circuit that includes the driving power supply and the ECelement, switching between the two resistors. The resistivity of theresistor R1 can be smaller than at least the highest impedance in theclosed circuit including the element, preferably 1Ω or less. Theresistivity of the resistor R2 can be greater than the highest impedancein the closed circuit including the element, preferably 1 MΩ or more.

The resistor R2 can be regarded as air. In this case the closed circuitis an open circuit, to be exact. However, this open circuit isequivalent to a closed circuit when air is regarded as the resistor R2.

The adjusting controller 10 controls the voltages V1 and V2 at thedriving power supply 8 and the switching between the resistors R1 and R2at the resistor switch 9. A specific example of the structure of theadjusting controller 10 includes controller A and controller B.Controller A is configured to saturate a change in the transmittance ofthe element to reset the element to an initial state by applying thevoltage which resets the element to the initial state, and controller Bis configured to control the tone of the element by applying the voltagewhich adjusts the transmittance of the element following controller A.

The following describes two specific forms of control with the adjustingcontroller 10, (1) for a case where an organic EC material that formscation through oxidation is used, and (2) for a case where an organic ECmaterial that forms anion through reduction is used. In the form ofcontrol (1), in which oxidation and back reduction are used, how high orlow the voltages V1 and V2 are is considered in the same direction aspositivity, i.e., voltage is higher with increasing positivity. Avoltage higher than the oxidation voltage therefore represents a voltagemore positive than the oxidation voltage. In the form of control (2), inwhich reduction and back oxidation are used, how high or low thevoltages V1 and V2 are is considered in the same direction asnegativity. A voltage higher than the reduction voltage thereforerepresents a voltage more negative than the reduction voltage.

In another specific form of control (1) with the adjusting controller10, controller A applies voltage V1 to saturate a change in thetransmittance of the element to reset the element to the initial state,and controller B, following controller A, applies voltage V2 higher thanvoltage V1 and not lower than the oxidation voltage if voltage V1 isequal to or lower than the back reduction voltage, or applying voltageV2 lower than voltage V1 and not higher than the back reduction voltageif voltage V1 is equal to or higher than the oxidation voltage, connectsthe resistor R1 in series in the element-containing closed circuit for aduration T1, and connects the resistor R2, which is of higherresistivity than the resistor R1, in series in the element-containingclosed circuit for a duration T2 to reduce the circuit current, andcontroller B continuously alternates connecting the resistor R1 for theduration T1 and connecting the resistor R2 for the duration T2 while inoperation.

In another specific form of control (2) with the adjusting controller10, controller A applies voltage V1 to saturate a change in thetransmittance of the element to reset the element to the initial state,and

controller B, following controller A, applies voltage V2 higher thanvoltage V1 and not lower than the reduction voltage if voltage V1 isequal to or lower than the back oxidation voltage, or applying voltageV2 lower than voltage V1 and not higher than the back oxidation voltageif the V1 is equal to or higher than the reduction voltage,

connects the resistor R1 in series in the element-containing closedcircuit for a duration T1, and

connects the resistor R2, which is of higher resistivity than theresistor R1, in series in the element-containing closed circuit for aduration T2 to reduce the circuit current, and

controller B continuously alternates connecting the resistor R1 for theduration T1 and connecting the resistor R2 for the duration T2 while inoperation.

Controller B is configured to adjust the transmittance of the element bychanging T1 with the total duration (T1+T2) constant, where T1 is theduration for which the resistor R1 is in the connected state and T2 isthe duration for which the resistor R2 is in the connected state.

The duration (T1+T2) can be 100 milliseconds or less.

The aforementioned EC materials are those that switches between aneutral state and cation upon oxidation and back reduction. It is alsopossible to use an EC material that switches between a neutral state andanion upon reduction and back oxidation, instead of oxidation and backreduction, respectively.

A method according to an aspect of the invention for driving anelectrochromic (EC) element is a method designed to adjust thetransmittance of a solution-type electrochromic element to allow theelement to display a desired tone. The element has a pair of electrodesand at least one organic electrochromic material mixed between theelectrodes.

The method includes adjusting the transmittance of the element(adjustment). The adjustment includes saturating a change in thetransmittance of the element to reset the element to the initial state(saturation) and controlling the transmittance (control).

The following describes two specific forms of control in the adjustment,(3) for a case where an organic EC material that forms cation throughoxidation is used, and (4) for a case where an organic EC material thatforms anion through reduction is used. In the form of control (3), inwhich oxidation and back reduction are used, how high or low thevoltages V1 and V2 are is considered in the same direction aspositivity, i.e., voltage is higher with increasing positivity. Avoltage higher than the oxidation voltage therefore represents a voltagemore positive than the oxidation voltage. In the form of control (4), inwhich reduction and back oxidation are used, how high or low thevoltages V1 and V2 are is considered in the same direction asnegativity. A voltage higher than the reduction voltage thereforerepresents a voltage more negative than the reduction voltage.

In another specific form of control (3) in the adjustment, thesaturation includes applying voltage V1 to saturate a change in thetransmittance of the element to reset the element to the initial state,and the control, following the saturation, includes applying voltage V2higher than voltage V1 and not lower than the oxidation voltage ifvoltage V1 is equal to or lower than the back reduction voltage, orapplying voltage V2 lower than voltage V1 and not higher than the backreduction voltage if voltage V1 is equal to or higher than the oxidationvoltage, connecting the resistor R1 in series in the element-containingclosed circuit for a duration T1, and connecting the resistor R2, whichis of higher resistivity than the resistor R1, in series in theelement-containing closed circuit for a duration T2 to reduce thecircuit current, wherein connecting the resistor R1 for the duration T1and connecting the resistor R2 for the duration of T1 continuouslyalternate while the control proceeds.

In another specific form of control (4) in the adjustment, thesaturation includes applying voltage V1 to saturate a change in thetransmittance of the element to reset the element to the initial state,and

the control, following the saturation, includes applying voltage V2higher than voltage V1 and not lower than the reduction voltage ifvoltage V1 is equal to or lower than the back oxidation voltage, orapplying voltage V2 lower than voltage V1 and not higher than the backoxidation voltage if the V1 is equal to or higher than the reductionvoltage,

connecting the resistor R1 in series in the element-containing closedcircuit for a duration T1, and

connecting the resistor R2, which is of higher resistivity than theresistor R1, in series in the element-containing closed circuit for aduration T2 to reduce the circuit current, wherein

connecting the resistor R1 for the duration T1 and connecting theresistor R2 for the duration of T1 continuously alternate while thecontrol proceeds.

The control includes adjusting the transmittance of the element bychanging T1 with the total duration (T1+T2) constant, where T1 is theduration for which the resistor R1 is in the connected state and T2 isthe duration for which the resistor R2 is in the connected state.

In an embodiment of the invention, at least one of the multiple organicelectrochromic materials may have an optical absorption peak differentfrom that of the other organic electrochromic materials.

Furthermore, at least one of the multiple organic electrochromicmaterials may have an optical absorption peak in the wavelength rangefrom 440 nm to 490 nm or the wavelength range from 540 nm to 630 nm.

Moreover, at least one of the organic electrochromic material may beselected from compounds (1) to (4) represented by the followingstructural formulae.

A driver according to an aspect of the invention allows the user toprovide an optical filter, an imaging device, a lens unit, and a windowcomponent in which a driver for an electrochromic element is used thatallows the element to display a desired tone causing no change in theshape of the absorption spectrum.

An optical filter according to an aspect of the invention has theelectrochromic element described above and a driver configured tocontrol the electrochromic element.

The optical filter may be used in an imaging device, such as a camera.When used in an imaging device, the optical filter may be provided tothe body of the imaging device or a lens unit.

An imaging device according to an aspect of the invention has thisoptical filter and a light-receiving element configured to receive lightafter the light passes through the optical filter.

A lens unit according to an aspect of the invention has an opticalsystem including multiple lenses and also has the aforementioned opticalfilter, and the arrangement is such that light should pass through theoptical system after passing through the optical filter.

Another lens unit according to an aspect of the invention has an opticalsystem including multiple lenses and also has the aforementioned opticalfilter, and the arrangement is such that light should pass through theoptical filter after passing through the optical system.

A window component according to an aspect of the invention has theaforementioned driver for an electrochromic element and a circuitconfigured to supply the driver with driving voltage.

The following describes an embodiment of an imaging device and a lensunit in which an optical filter according to an aspect of the inventionis used.

FIG. 9 is a schematic diagram that illustrates a lens unit in which anoptical filter according to an aspect of the invention is used and animaging device that has this lens unit.

An optical filter 101 has an organic EC element and an active elementconnected to the organic EC element and is located in a lens unit 102.

The lens unit 102 is a unit that includes multiple lenses or groups oflenses. For example, the lens unit in FIG. 9 represents a rear-focusingzoom lens, i.e., a zoom lens that focuses behind the diaphragm, and hasfour groups of lenses, a first lens group 104 with a positive refractivepower, a second lens group 105 with a negative refractive power, a thirdlens group 106 with a positive refractive power, and a fourth lens group107 with a positive refractive power in this order from the from theobjective side. The user changes the distance between the second groupand the third group to change the magnification and moves some of thelenses in the fourth group to focus.

The lens unit 102 has, in an illustrative structure, an aperture stop108 between the second group and the third group and also has an opticalfilter 101 between the third group and the fourth group.

The arrangement is such that light that passes through the lens unitshould pass through the lens groups, the diaphragm, and the opticalfilter. The amount of light can therefore be adjusted with the aperturestop and the optical filter.

The internal structure of the lens unit can be modified as necessary.For example, the optical filter may be disposed in front of or behindthe aperture stop, and it is also possible to place the optical filterin front of (i.e., on the objective side with respect to) the firstgroup or behind the fourth group. Placing the optical filter in thepoint where light converges is advantageous in that, for example, itallows the optical filter to be smaller in size.

The format of the lens unit can also be selected as appropriate. Besidesa rear-focusing lens, the lens unit can be an inner-focusing lens, i.e.,a lens that focuses in front of the diaphragm, or any other format oflens. Specialized lenses such as a fisheye lens and a macro lens canalso be chosen in addition to a zoom lens, if necessary.

The lens unit is detachably connected to an imaging device 103 through amount (not illustrated).

A glass block 109 is a glass block that can be a low-pass filter, aphase plate, or a color filter, for example.

A light-receiving element 110 is a sensor that receives light after thelight has passed through the lens unit. CCD, CMOS, and other imagepickup elements can be used. The light-receiving element 110 can also bea photosensor, such as a photodiode. An element that collectsinformation on the intensity or wavelength of the light and outputs itcan be used as appropriate.

When the optical filter is incorporated in the lens unit as in FIG. 9,it is not necessary that a vibration mechanism be bonded to theelectrochromic element used as the optical filter. For example, it ispossible to use the optical filter with an actuator mechanism with whichthe lens unit is operated. The movement of the lens groups can be donewith the use of an electromagnetic motor or an ultrasonic motor.Transmitting vibration of such a motor to the optical filter hasstirring effects on the solution, i.e., the organic EC layer describedin Examples, improving the response speed of the element particularly byenhancing the responsiveness to erasing.

The imaging device itself may have the optical filter 101. FIG. 10 is aschematic view of an imaging device that has an optical filter.

The optical filter is located in an appropriate position in the imagingdevice, and a light-receiving element 110 can be located in any positionwhere it receives light after the light has passed through the opticalfilter. In FIG. 10 the optical filter is located immediately in front ofthe light-receiving element. Incorporating the optical filter in animaging device itself provides the imaging device with a light controlcapability and also allows the imaging device to be used with anexisting lens unit because in this case it is not necessary that theattached lens unit itself have the optical filter.

Such an imaging device can be applied to products in which adjustment ofthe amount of light is combined with a light-receiving element. Forexample, such an imaging device can be used in cameras, digital cameras,camcorders, and digital camcorders. It is also possible to use such animaging device to a product that incorporates an imaging device, e.g., acellular phone, a smartphone, a PC, or a tablet computer.

The use of an optical filter based on an organic EC element as a lightcontroller as in this embodiment allows the user to vary the amount oflight control with one filter as appropriate, offering advantages suchas the reduction of components in number and size. The use of theoptical filter disclosed herein also is also advantageous in that itallows for halftone control and improves responsiveness, for example.

FIGS. 11A and 11B illustrate a window component that has an EC elementaccording to this embodiment. The window component can be used to makewindows of houses, automobiles, airplanes, and so forth.

EXAMPLES

The following describes some embodiments of the invention with referenceto drawings.

Example 1

This example describes the control of transmittance by taking materialswhose neutral species turns into cation developing a color uponoxidation as illustrative organic EC materials, assuming that theinitial state of an EC element (the state of the element afterresetting) is a substantially colorless state.

Research by the inventors has found that the absorption spectrum of amaterial that forms an assembly like that described in theaforementioned non-patent document varies because the behavior ofabsorption changes of the radical species and the assembly duringcoloring is different from that during erasing. An example of alow-molecular-weight organic EC material that forms an assembly iscompound 1.

FIGS. 3A and 3B illustrate changes in transmittance on an absorptionspectrum of a solution of compound 1 and a supporting electrolyte (TBAP)in solvent propylene carbonate during coloring and erasing,respectively. The concentration of compound 1 is 10 mM, and theconcentration of TBAP is 0.1 M. The EC element has a structure in whichtwo glass ITO substrates are joined together with 150-μm spacerstherebetween and the space defined by the substrates and the spacersfilled with a solution that contains the organic EC material. A voltageof 2 V was applied across the electrodes to color the compound, and 0 Vwas applied to erase the color of the compound. In FIGS. 3A and 3B awavelength of 530 nm seems to be an absorption peak corresponding to thecationic species of compound 1, and a wavelength of 496 nm seems to bean absorption peak corresponding to an assembly formed by the cationicspecies. The changes in the ratio between the two absorption peaksindicate that the absorption by the assembly tends to fall rapidlyduring erasing, the absorption ratio greatly varying between coloringand erasing. It is therefore difficult to control the tone whilemaintaining the absorption spectra in both directions, i.e., thecoloring direction and the erasing direction, when using a material thatforms an assembly.

Mixing multiple organic EC materials to express a given color toneresults in the ratios of the amount of optical absorption between thematerials during coloring upon application of the oxidation voltagebeing different from those upon application of the back reductionvoltage because the oxidation voltage and the back reduction voltage aredifferent for the specific materials. In general, the tendency of amaterial toward oxidation and back reduction depends on the state ofpolarization (overvoltage) with respect to the oxidation voltage and theback reduction voltage as shown in Equation 1. The overvoltage refers tothe difference between the oxidation voltage or the back reductionvoltage of the material and the voltage applied to the electrodes thatacts on the material. In Equation 1, the term i is the current densityof the reaction, i₀ is exchange current density, α is the chargetransfer coefficient, n is the number of electrons involved in thereaction, F is the Faraday constant, η is overvoltage, R is the gasconstant, and T is temperature. The term i₀ has the relationship givenin Equation 2. In Equation 2, k⁰ is the reaction velocity constant, c₀is the concentration of the oxidized form, and c_(R) is theconcentration of the reduced form.

$\begin{matrix}{i = {i_{0}\left\lbrack {{\exp \left( \frac{\alpha \; {nF}\; \eta}{RT} \right)} - {\exp \left( \frac{{- \left( {1 - \alpha} \right)}{nF}\; \eta}{RT} \right)}} \right\rbrack}} & \left( {{Equation}\mspace{14mu} 1} \right) \\{i_{0} \equiv {{nFk}^{0}c_{O}^{({1 - \alpha})}c_{R}^{\alpha}}} & \left( {{Equation}\mspace{14mu} 2} \right)\end{matrix}$

In general, upon application of a voltage at which multiple materialsare oxidized together, the material with the lowest oxidation voltage ofmultiple materials is most likely to allow the current to occur thatflows during the oxidation between the materials. On the other hand, ata voltage at which multiple materials are reduced back together, thematerial with the lowest back reduction voltage is most unlikely toallow current to occur during the back reduction between the materials.

Separately, Equation 1 indicates that electrochemical reaction dependson overvoltage if the temperature and the concentrations are constant.This means that the amount of each material involved in the reaction onthe surface of the electrode is constant if the overvoltage, i.e., thevoltage applied to the EC element, is constant. The total amount ofmaterial involved in the reaction is also constant because it depends onthe amount of material supplied to the surface of the electrode, i.e.,the diffusion constant of the materials. Consequently, it is possible tocolor the EC element with uniform absorption ratios between thematerials by oxidizing (coloring) the EC element when it is in theinitial state.

FIGS. 4A and 4B are diagrams that illustrate absorption spectra of an ECelement that contains multiple materials, the EC element driven at afixed voltage. FIG. 4A is a diagram that illustrates changes with timein transmittance on an absorption spectrum upon application of a fixedvoltage to four materials, compound 1 and compounds 2, 3, and 4.

The element structure is the same as that in the measurementsillustrated in FIGS. 3A and 3B except that the concentrations ofcompounds 1, 2, 3, and 4 were 2 mM, 8 mM, 13 mM, and 30 mM,respectively. This diagram illustrates changes in absorption at anapplied voltage of 2 V as changes in transmittance with the initialstate as reference, indicating that the transmittance decreases with theduration of application corresponding to specific tones. The absorptionspectrum in FIG. 4A is a combination of the absorption spectra of thefour materials. Compound 1 strongly absorbs light at 496 nm and 530 nm,compound 2 at 500 nm and 630 nm, compound 3 at 440 nm and 490 nm, andcompound 4 at 540 nm and 600 nm. The absorption at 440 nm, 490 nm, 540nm, and 630 nm in FIG. 4A reflects the strong absorption by theindividual materials.

FIG. 4B is an overlay of the absorption spectrum for the durations inFIG. 4A obtained through the conversion of transmittance into absorbanceand normalization with the absorbance at 630 nm as 1. Arelationship−Log(Transmittance)=Absorbance holds between transmittanceand absorbance. Lambert-Beer's law indicates that absorbance has therelationship Absorbance=Molar absorptivity× Concentration of thematerial× Path length of the light. Because of the linearity between thechange in absorbance resulting from coloring and the change in theconcentration of cation, it is preferred to use absorbance to discusswhether the individual forms of the absorption spectrum agree in shape.

FIG. 4B indicates good agreement in absorbance between the individualforms of the absorption spectrum, demonstrating that an EC element thatcontained multiple materials was driven successfully, causing no changein the shape of the absorption spectrum, by application of a fixedvoltage.

It is therefore possible to drive an EC element, causing no change inthe shape of the absorption spectrum, by applying a fixed voltage whendriving the EC element in the coloring direction from the initial state.

This means that a driver configured to control the tone of an EC elementsuccessfully changes the tone of an EC element when the driver resetsthe EC element to the initial state and then operates in a mode of drivein which the driver applies a fixed voltage to set the EC element at thenext (desired) tone. Such a driver allows an EC element to display adesired tone causing no change in the shape of the absorption spectrumeven when the EC element contains multiple materials with differentredox potentials.

In research by the inventors the use of a form of drive control likethat illustrated in FIG. 5 allows a tone condition to be maintainedcausing no change in the shape of the absorption spectrum.

FIG. 5 illustrates voltages V1 and V2 that are applied to an EC element,resistors R1 and R2 that are connected to a closed circuit that includesthe EC element, durations T1 and T2 for which the resistors R1 and R2are connected, and an associated change in transmittance.

The following describes a case in which an EC element is driven thatcontains a mixture of compounds 1 to 4 used in FIGS. 4A and 4B.Compounds 1 to 4 are colored upon application of the oxidation voltageand turn colorless upon application of the back reduction voltage. Theinitial state (reset state) is the colorless state, the back reductionvoltage is V1, and the oxidation voltage is V2. What resets the ECelement to the initial state is controller A, and what sets it at thenext tone following controller A is controller B.

Controller B continuously repeats connecting the resistor R1 to theclosed circuit that includes the element for the duration T1 with theoxidation voltage V2 applied and connecting the resistor R2 for theduration T2.

The resistor R1 is of low resistivity, and connecting R1 makes oxidationmore likely to occur by allowing current to flow in the closed circuit.The resistor R2 is of high resistivity, and connecting R2 makesoxidation less likely to occur by preventing current from flowing in theclosed circuit.

In general, it is known that in an EC element in which a dissolvedorganic material is used as EC material, the cation resulting fromoxidation returns to the neutral state because of self-erasing when leftin an open-circuit state (equivalent to a closed circuit when connectedwith the air, a high-resistivity material).

The change in transmittance is therefore controlled through the controlof the ratio of the duration T1 with the total duration (T1+T2)constant, where T1 is the duration for which oxidation proceeds and T2is the duration for which self-erasing proceeds. Increasing the ratio ofthe duration T1 increases the change in transmittance, and reducing theratio of the duration T1 reduces the change in transmittance.

When a tone is changed to the next tone, the shape of the absorptionspectrum can be maintained by once resetting the element to the initialstate with controller A and then controlling the tone with controller B.

The voltages V1 and V2 are fixed voltages applied by a driving powersupply. The connection between the EC element and the driving powersupply is controlled with a relay circuit (an analog switch circuit or atransistor circuit) that is a resistor switch. The analog switch circuitswitches the connection of the driving power supply with the EC elementbetween the connected state and the disconnected state. The time pointsof the control with the analog switch circuit were programmed throughsupply with voltage from an arbitrary waveform generator. The arbitrarywaveform generator corresponds to a portion of the functionality of theadjusting controller. The operation of the analog switch circuit issimilar to connecting a low-resistivity resistor and a high-resistivityresistor to the wiring of the EC element in series. In this case thelow-resistivity resistor can be regarded as the resistivity of thewiring material and is on the order of mΩ, and the high-resistivityresistor is the air and greatly exceeds MΩ.

Switching the circuit including the element between low resistivity andhigh resistivity in this way controls the amount of current that flowsin the circuit. Connecting the circuit to the low-resistivity resistorallows current to flow and oxidation to occur, coloring the EC element.Connecting the circuit to the high-resistivity resistor stops currentfrom flowing and prevents oxidation from occurring, during which theorganic EC materials diffuse and self-erase their colors.

Assuming that the initial state (the state after resetting) is asubstantially colorless state, continuously switching the connection tothe resistors R1 and R2 after the durations T1 and T2 while applying theoxidation voltage (V2) to the element in the initial state usingcontroller B leads to a gradual rise in the overall color and anincrease in absorption in the early period of oxidation because in thisperiod the concentration of the neutral species is extremely high in thevicinity of the electrode and thus oxidation is dominant, exceeding thedecrease in color associated with self-erasing (hereinafter simplyreferred to as the self-erasing). Once the increase in color has reacheda certain extent, the concentration of the neutral species in thevicinity of the electrode is low and the oxidation has accordinglydiminished, whereas the self-erasing is great because the concentrationof the cationic species has increased. The balance between the colorincrease and the self-erasing gradually becomes even in this way. Nearthe concentration equilibrium point, at which an even balance isreached, the transmittance of the EC element stabilizes and the tone ismaintained.

Increasing the ratio of the low-resistivity resistor connection to thetotal of the durations T1 and T2 (T1+T2), i.e., T1/(T1+T2), which meansincreasing the duration for which the circuit is connected to thelow-resistivity resistor, enhances the color increase and reduces theself-erasing. This shift of the concentration equilibrium point towardgreater increase in color leads to the EC element maintaining a greaterchange in transmittance. In contrast, reducing the duration for whichthe circuit is connected to the low-resistivity resistor reduces thecolor increase and enhances the self-erasing. This shift of theconcentration equilibrium point toward smaller increase in color leadsto the EC element maintaining a smaller change in transmittance.

FIG. 6 illustrates time courses of a transmittance at a singlewavelength of 630 nm during an operation of the EC element used in FIGS.4A and 4B, which contained a mixture of compounds 1 to 4, according tothe form of drive control in FIG. 5.

FIG. 6 is a continuous repeat of the connection to the resistors R1 andR2 conducted while applying an oxidation voltage (V2) of 1.7 V to anelement in the initial state (the state after resetting) with the totalof the durations T1 and T2 (T1+T2) fixed at 100 Hz (10 msec),illustrating time courses of a transmittance at a single wavelength of630 nm during a 300-second operation with controller B with the ratio ofthe low-resistivity resistor connection to the total of the durations T1and T2 (T1+T2), i.e., T1/(T1+T2), set at 0.1%, 0.3%, 0.8%, 2%, and 10%.As can be seen from FIG. 6, adjusting the ratio of the low-resistivityresistor connection in the form of drive control described in thisexample successfully controlled and maintained the magnitude of a changein the transmittance of an EC element.

This means that a driver configured to control the tone of an EC elementsuccessfully changes the tone of an EC element when the driver resetsthe EC element to the initial state and then operates in a form of drivecontrol in which the element circuit switches between low resistivityand high resistivity while supplied with a fixed voltage to set the ECelement at the next (desired) tone. Such a driver allows an EC elementto display a desired tone causing no change in the shape of theabsorption spectrum even when the EC element contains a material thatforms an assembly or multiple materials with different redox potentials.

Example 2

This example describes the control of transmittance by taking materialswhose neutral species turns into cation developing a color uponoxidation as illustrative organic EC materials, assuming that theinitial state of an EC element (the state of the element afterresetting) is a state in which the transmittance of the EC element issmall as a result of coloring.

FIG. 7 illustrates voltages V1 and V2 that are applied to an EC element,resistors R1 and R2 that are connected to a closed circuit that includesthe EC element, durations T1 and T2 for which the resistors R1 and R2are connected, and an associated change in transmittance.

The following mentions a case in which an EC element is driven thatcontains a mixture of compounds 1 to 4 used in FIGS. 4A and 4B.Compounds 1 to 4 are colored upon application of the oxidation voltageand turn colorless upon application of the back reduction voltage. Theinitial state (reset state) is the colored state, the oxidation voltageis V1, and the back reduction voltage is V2. What resets the EC elementto the initial state is controller A, and what sets it at the next tonefollowing controller A is controller B.

Controller B continuously repeats connecting the resistor R1 to theclosed circuit that includes the element for the duration T1 with theback reduction voltage V2 applied and connecting the resistor R2 for theduration T2.

The resistor R1 is of low resistivity, and connecting R1 makes backreduction more likely to occur by allowing current to flow in the closedcircuit. The resistor R2 is of high resistivity, and connecting R2 makesback reduction less likely to occur by preventing current from flowingin the closed circuit.

In general, it is known that in an EC element in which a dissolvedorganic material is used as an EC material, the cation resulting fromoxidation returns to the neutral state because of self-erasing when leftin an open-circuit state (equivalent to a closed circuit when connectedwith the air, a high-resistivity material). Making V2 more negativetherefore back-reduces most of the EC material, resetting it to theneutral state. In electrochemical measurement, however, a region ispresent between oxidation and back reduction where both reactions aresimultaneously initiated, extending over a voltage range of 60 mV toseveral hundred millivolts. The use of a voltage at which back reductionis slightly dominant to oxidation as back reduction voltage allows fortone control with a smaller amount of the material back-reduced.

The change in transmittance is therefore controlled through the controlof the ratio of the duration T1 with the total duration (T1+T2)constant, where T1 is the duration for which back reduction proceeds andT2 is the duration for which back reduction stops. Increasing the ratioof the duration T1 increases the change in transmittance, and reducingthe ratio of the duration T1 reduces the change in transmittance.

Tone control during which the shape of the absorption spectrum ismaintained can be done by first resetting the element to the initialstate with controller A and then controlling the tone with controller B.

Example 3

This example describes the control of transmittance by taking a materialwhose neutral species turns into anion developing a color upon reductionas an illustrative organic EC material, assuming that the initial stateof an EC element (the state of the element after resetting) is a statein which the transmittance of the EC element is large as a result oferasing.

FIG. 8 illustrates voltages V1 and V2 that are applied to an EC element,resistors R1 and R2 that are connected to a closed circuit that includesthe EC element, durations T1 and T2 for which the resistors R1 and R2are connected, and an associated change in transmittance.

Examples of EC materials that form anion include anthraquinone dyes.

Anthraquinone is colored upon application of the reduction voltage andturns colorless upon application of the back oxidation voltage. Theinitial state (reset state) is the colorless state, the back oxidationvoltage is V1, and the reduction voltage is V2. What resets the ECelement to the initial state is controller A, and what sets it at thenext tone following controller A is controller B.

Controller B continuously repeats connecting the resistor R1 to theclosed circuit that includes the element for the duration T1 with thereduction voltage V2 applied and connecting the resistor R2 for theduration T2.

The resistor R1 is of low resistivity, and connecting R1 makes reductionmore likely to occur by allowing current to flow in the closed circuit.The resistor R2 is of high resistivity, and connecting R2 makesreduction less likely to occur by preventing current from flowing in theclosed circuit.

In general, it is known that in an EC element in which a dissolvedorganic material is used as an EC material, the anion resulting fromreduction returns to the neutral state because of self-erasing when leftin an open-circuit state (equivalent to a closed circuit when connectedwith the air, a high-resistivity material).

The change in transmittance is therefore controlled through the controlof the ratio of the duration T1 with the total duration (T1+T2)constant, where T1 is the duration for which reduction proceeds and T2is the duration for which reduction stops. Increasing the ratio of theduration T1 increases the change in transmittance, and reducing theratio of the duration T1 reduces the change in transmittance.

Tone control during which the shape of the absorption spectrum ismaintained can be done by first resetting the element to the initialstate with controller A and then controlling the tone with controller B.

A driver according to an aspect of the invention for an electrochromicelement, which allows the element to display a desired tone and maintainthe tone causing no change in the shape of the absorption spectrum, canbe used in optical filters, in particular, a neutral density (ND) filterfor cameras.

Certain aspects of the invention provide a driver for an electrochromicelement that allows the element to display a desired tone causing nochanges in the shape of the absorption spectrum, a method for driving anelectrochromic element with such a driver, an optical filter, an imagingdevice, a lens unit, and a window component.

While the present invention has been described with reference toexemplary embodiments, it is to be understood that the invention is notlimited to the disclosed exemplary embodiments. The scope of thefollowing claims is to be accorded the broadest interpretation so as toencompass all such modifications and equivalent structures andfunctions.

What is claimed is:
 1. An electrochromic element comprising: a pair ofelectrodes; an electrochromic layer disposed between the pair ofelectrode; the electrochromic layer comprising two kinds of organiccompounds; and a driver connected to at least one of the pair ofelectrodes, wherein the driver increases transmittance of theelectrochromic element with applying a voltage before decreasing thetransmittance of the electrochromic element.
 2. The electrochromicelement according to claim 1, wherein: the driver is configured tosaturate a change in the transmittance of the electrochromic element byapplying a voltage V1, the V1 is a voltage which is equal to or higherthan an oxidation voltage of one of the organic compounds, and which islower than a back reduction voltage of the other organic compounds. 3.The electrochromic element according to claim 1, wherein the driver isconfigured to increase the transmittance of the electrochromic elementby pulse width modulation.
 4. The electrochromic element according toclaim 3, wherein a period of the pulse width modulation is 100milliseconds or less.
 5. The electrochromic element according to claim1, wherein one of the organic compounds has an optical absorption peakdifferent from an optical absorption peak of the other organic compound.6. The electrochromic element according to claim 5, wherein the organiccompound has an optical absorption peak in a wavelength range from 440nm to 490 nm or a wavelength range from 540 nm to 630 nm.
 7. An imagingdevice comprising the electrochromic element according to claim 1 and alight-receiving element configured to receive light after the light haspassed through the electrochromic element.
 8. The electrochromic elementaccording to claim 1, wherein: the electrochromic layer is asolution-type electrochromic layer
 9. The electrochromic elementaccording to claim 1, wherein a difference between oxidation potentialsof the two kinds of organic compounds is within 60 mV.
 10. Theelectrochromic element according to claim 1, wherein the driver connectsa resistor R1 and the electrochromic element for a duration ofdecreasing the transmittance of the electrochromic element and connectsa resistor R2 of higher resistivity than the resistor R1 and theelectrochromic element for a duration of increasing the transmittance ofthe electrochromic element.